We report here on the properties of topological crystalline insulator Pb_0.5Sn_0.5Te epitaxial films doped with bismuth at levels from 0% (undoped) to 0.15%. The undoped film exhibits a p-type character due to metal vacancies. As the doping level rises, the hole concentration reduces. At a level of 0.06%, the electrical character inverts to n-type and the electron density continues to increase for rising doping level up to 0.15%. This result demonstrates an effective extrinsic n-type doping of Pb_0.5Sn_0.5Te crystal with bismuth due to substitutional Bi atoms in metal sites. High-resolution x-ray diffraction and reciprocal space mapping show that fully relaxed high-quality films are obtained. A pristine (111) film surface is revealed after removal of the Te cover layer using a method combining Ar⁺ sputtering and thermal desorption. Angle-resolved photoemission spectroscopy (ARPES) data acquired at 30 K near the [Formula: see text] point of the undoped film surface show a parabolic-like dispersion of the bulk valence band close to the Fermi level. Now, the ARPES data for a sample doped with 0.1% of Bi reveal that the chemical potential is shifted by 40 meV upwards in the direction of the conduction band. The ARPES results also indicate that there might be a discrepancy between surface and bulk chemical potential in the doped sample. This divergence suggests that Te atoms diffuse into the surface during the thermal process to desorb the protective layer, inverting the surface to p-type.